WO2010063741A1 - Aldimine and composition containing aldimine - Google Patents

Abstract

The invention relates to aldimines of formula (I), of use as latent hardeners, in particular in moisture-hardening polyurethane compositions containing isocyanate groups. The aldimines are mostly liquid compounds at room temperature with good storage resistance with hardly noticeable aldehyde odours after hardening. In particular, the aldehyde groups released on hydrolysis in the polyurethane compositions have a small softening effect and hardly tend to migrate or exudate.

Description

 ALDIMINE AND ALDIMINE CONTAINING COMPOSITION

Technical area

The invention relates to the field of aldimines and the field of polyurethane compositions and their use, in particular as an adhesive, sealant, coating or floor covering.

State of the art

Aldimines are condensation products of primary amines and aldehydes and represent a well-known class of compounds. Upon contact with moisture, aldimines can hydrolyze to the corresponding amines and aldehydes. Due to this peculiarity, they can be used as a protected form of amines, or of aldehydes. For example, aldimines are used in polyurethane chemistry, where they serve as moisture-activatable crosslinkers, so-called "blocked amines" or "latent hardeners", for one- or two-component isocyanate-containing compositions.

The advantages of using aldimines as latent hardeners in isocyanate-containing systems are, in particular, that the formation of undesirable gas bubbles can be avoided, since the curing reaction via the blocked amine - in contrast to the direct reaction of isocyanates with moisture - not to release carbon dioxide (CO2), and that higher cure rates and / or longer open times can be achieved. However, the use of aldimines as latent hardeners in compositions containing isocyanate groups can also cause problems. In the case of one-component compositions, the storage stability can be severely limited by the presence of aldimine. In addition, depending on the aldehyde used to make the aldimine and released in the curing reaction, the compositions may have a very strong odor which is intolerable to many applications.

WO 2004/013088 A1 describes odorless polyaldimines which are prepared from primary polyamines and odorless aldehydes. WO 2007/036571 A1 describes odorless aldimines containing at least one hydroxyl, mercapto or secondary amino group, which are likewise obtainable starting from odorless aldehydes. These odorless aldehydes can have a strong plasticizing effect in polymer compositions, especially in polyurethane compositions, which may be undesirable. The relatively high molecular weight of the aldehydes also means that the aldimines produced therefrom must be used as latent hardener in a relatively large amount, which can make their use expensive.

Presentation of the invention

It is therefore an object of the present invention to provide new aldimines which can be used as latent hardeners in curable compositions, in particular in moisture-curing, polyurethane compositions containing isocyanate groups.

Surprisingly, it has been found that aldimines according to claim 1 solve this problem and have advantageous properties. These are usually liquid at room temperature compounds which have little aldehyde odor before, during and after the hydrolysis. They have a good Lagerstabi ity together with isocyanate groups, especially with very reactive aromatic isocyanate groups. In their hydrolysis, an aldehyde is released, which is particularly well tolerated in polyurethane compositions, where it exerts only a low plasticizing effect and hardly prone to migration or exudation. They are therefore very well suited as latent hardeners in compositions containing isocyanate groups.

Further aspects of the invention are the subject of further independent claims. Particularly preferred embodiments of the invention are the subject of the dependent claims. Ways to carry out the invention

An object of the invention is an aldimine of the formula (I)

in which

Y is O or S; A is either the radical of an amine after removal of n primary amino groups and m HX groups, or together with R ^{7 is} an (n + 2 * m) -valent hydrocarbon radical having 3 to 20 C atoms, which optionally has at least one heteroatom , in particular in the form of ether oxygen or tertiary amine nitrogen; n is 1 or 2 or 3 or 4 and m is 0 or 1 or 2 or 3 or 4, with the proviso that m + n is 2 or 3 or 4 or 5;

R ¹ and R ² are each, independently of one another, each a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 4 to 12 C atoms, the part of an optionally substituted, carbocyclic ring with 5 to 8, preferably 6, C atoms are; R ^{3 represents} a hydrogen atom or an alkyl, cycloalkyl, arylalkyl or alkoxycarbonyl radical having 1 to 12 C atoms; R ⁴ and R ^{5 are} either together for an optionally oxygen or sulfur atoms having divalent radical having 2 to 10 carbon atoms, which is part of an optionally substituted, 5- or 6- or 7-membered ring, are, or

R ^{4 is} an alkyl, cycloalkyl, arylalkyl or acyl radical having 1 to 10 C atoms, and R ^{5 is} a hydrogen atom or a monovalent radical having 1 to 20 C atoms selected from the group consisting of alkyl, cycloalkyl, arylalkyl, aryl radical, -OR ^{5 '} , -SR ^5' and -NR ⁵ R ^{5 "} , wherein R ^{5 '} and R ^5" are each either a hydrocarbon radical or together an alkylene radical which is part of a 5-, 6- or 7-membered ring; X is O or S or NR ⁶ or NR ⁷ , where R ^{6 is} either a monovalent hydrocarbon radical having 1 to 20 C

Atoms which optionally contain at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid ester

Has, or stands for a substituent of the formula (II),

where p is 0 or an integer from 1 to 10OOO, and B is a (p + 1) -valent hydrocarbon radical which is optionally ether-oxygen, tertiary-amine-nitrogen,

Contains hydroxyl groups, secondary amino groups or mercapto groups; and

R ⁷ together with A for a (n + 2 * m) -valent hydrocarbon radical having 3 to 20 C-atoms, which optionally at least one

Heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen contains.

The dashed lines in the formulas in this document each represent the bond between a substituent and the associated moiety.

The term "primary amino group" as used herein refers to an amino group in the form of an NH ₂ group attached to an organic radical. denotes an amino group in which the nitrogen atom is bonded to two organic radicals which may also together be part of a ring. The term "tertiary amino group" denotes an amino group in which the nitrogen atom (= tertiary amine nitrogen) is bonded to three organic radicals, wherein two of these radicals may also together be part of a ring.

The term "active hydrogen" in the present document denotes the hydrogen atom of a hydroxyl, a mercapto or a secondary or primary amino group.

As "aliphatic" is meant an amine and an isocyanate whose amino and isocyanate groups are each bound exclusively to aliphatic, cycloaliphatic or arylaliphatic radicals, correspondingly these groups are referred to as aliphatic amino and isocyanate groups.

By "aromatic" is meant an amine and an isocyanate, the amino and isocyanate groups of which are each bonded to an aromatic radical, and accordingly these groups are referred to as the aromatic amino and isocyanate groups.

A "low-odor" substance is understood to mean a substance whose odor is only slightly perceptible, ie, smelling, by human individuals, ie which does not have an intense odor, for example formaldehyde, acetaldehyde, isobutyraldehyde, or solvents such as acetone, methyl ethyl ketone or methyl isobutyl ketone , and this low odor is not perceived by most human individuals as unpleasant or offensive.

An "odor-free" substance is understood to mean a substance which is not palpable for most human individuals, ie which has no perceptible odor.

Preferably, R ¹ and R ² each represent a methyl radical. Preferably, R ^{3 is} a hydrogen atom.

Preferably, Y is an oxygen atom.

Preferably, R ^{4 is} a methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, cyclohexyl or benzyl radical and R ^{5 is} a hydrogen atom or a methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, cyclohexyl, benzyl, methoxy, ethoxy, propoxy or isopropoxy radical, or R ⁴ and R ⁵ together - including the nitrogen atom and the carbonyl or thiocarbonyl group - a ring, in particular a 2-pyrrolidone ring, a pyrrolidine-2,5-dione ring, a piperidine-2-one ring, a piperidine-2,6-dione Ring, an azepan-2-one ring, an oxazolidin-2-one ring or a thiazolidin-2-one ring, wherein such a ring is optionally substituted.

In one embodiment of the aldimines of the formula (I), m is 1 or

2 or 3 or 4, preferably for 1. Such aldimines thus have - based on the HX group - at least one active hydrogen.

Particularly preferred aldimines of the formula (I) with at least one active hydrogen are aldimines of the formula (Ia),

in which

A ^{1 is} either a divalent hydrocarbon radical having 2 to 20 C atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen, is, or together with R ^{9 is} a trivalent hydrocarbon radical with third to 20 carbon atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen;

X ^{1 is} O or S or NR ⁸ or NR ⁹ , where R ^{8 is} either a monovalent hydrocarbon radical having 1 to 20 C atoms which optionally contains at least one carboxylic acid ester, nitrile, Has nitro, phosphonic ester, sulfonic or sulfonic acid ester group, or stands for a substituent of the formula (II a),

wherein B ^{1 is} a bivalent, optionally ether oxygen or tertiary amine nitrogen having, hydrocarbon radical having 2 to 12 carbon atoms; and

R ⁹ together with A ^{1 represents} a trivalent hydrocarbon radical having 3 to 20 C atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen, and Y, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings already mentioned, with the proviso that A ^{1 has} no active hydrogen.

In a further embodiment of the aldimines of the formula (I), m is zero and n is 2 or 3 or 4. Such aldimines are polyaldimines. Substance names beginning with "poly", such as polyaldimine, polyamine or polyisocyanate, in the present document refer to substances which have formal containing two or more of the functional groups per molecule occurring in their name Particularly preferred aldimines of the formula (I) where m = 0

Aldimines of the formula (I b)

where t is 2 or 3;

A ^{2 is} the radical of an amine B2 after removal of t primary amino groups, and Y, R, R, R, R and R have the meanings already mentioned, with the proviso that the aldimine of the formula (I b) has no active hydrogen.

Aldimines of the formula (I) are obtainable from the reaction of at least one amine B of the formula (III) with at least one aldehyde ALD of the formula (IV),

HX ¹ '- ^ A- HMH ₂ (III)

J m L n

in which

X ^{a is} O or S or NR ^6a or NR ⁷ , wherein R ^{6a is} either a monovalent hydrocarbon radical of 1 to 20

C atoms which optionally contain at least one carboxylic ester,

Nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid ester group, stands, or represents a substituent of the formula (III '),

- B- ^ NH ₂ ] _{p (} " _r)

and m, n, A, B, Y, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and p have the meanings already mentioned.

The reaction between an amine B of the formula (III) and an aldehyde ALD of the formula (IV) is carried out in a condensation reaction with elimination of water. Such condensation reactions are well known and described, for example in Houben-Weyl, "Methods of Organic Chemistry", Vol. XI / 2, page 73ff., The aldehyde ALD is here stoichiomethsch in relation to the primary amino groups of the amine B or in stoichiometric Usually, such condensation reactions are carried out in the presence of a solvent, by means of in which the water formed in the reaction is removed azeotropically. For the preparation of the aldimines of the formula (I), however, a preparation process without the use of solvents is preferred, the water formed in the condensation being removed directly from the reaction mixture by applying a vacuum. Solvent-free production eliminates the need to distill off the solvent after production, which simplifies the production process. In addition, the aldimine is so free of solvent residues that could cause a disturbing smell.

As amine B of formula (III) are suitable in one embodiment

Compounds which, in addition to one or more primary amino groups, have at least one active hydrogen-bearing reactive group in the form of a hydroxyl, mercapto or secondary amino group. Examples of such amines B with more than one active hydrogen-bearing reactive group are

aliphatic amines containing more than one secondary amino group and one or more primary amino groups, such as N, N'-bis (3-aminopropyl) ethylenediamine, triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine and higher homologs of linear polyethyleneamines, N , N'-bis (3-aminopropyl) ethylenediamine, products of multiple cyanoethylation or cyanobutylation and subsequent hydrogenation of primary di- and polyamines having multiple primary amino groups, such as N, N'-bis (3-aminopropyl) ethylenediamine , N, N'-bis (3-aminopropyl) -1, 4-diaminobutane, N, N'-bis (3-aminopropyl) -2-methyl-1, 5-pentanediamine, N ₁ N'-bis (3-amino-1-ethylpropyl) -2-methyl-1, 5-pentanediamine and polyethylene imines of different degrees of polymerization (molar mass range 500 to 1 ¹ 000 ¹ 000 g / mol), as described for example under the trade name Lupasol ^® of BASF are available in pure form or as aqueous solutions, these polyethyleneimines addition of primary and secondary au ch tertiary amino groups contain;

- Hydroxyamine carrying more than one hydroxyl group and one or more primary amino groups, in particular derivatives of polyalkoxylated trihydric or higher alcohols or polyalkoxylated polyamines, as well as amino sugars, for example glucosamine or galactosamine; Hydroxypolyamines carrying at least one hydroxyl and at least one secondary amino group from the cyanoethylation or cyanobutylation and subsequent hydrogenation of hydroxyamines, such as N-hydroxyethyl-1,2-ethanediamine, N-hydroxypropyl-1,2-ethanediamine, N-hydroxyethyl - 1, 3-propanediamine, N3-hydroxyethyl-1, 3-pentanediamine.

As amine B of the formula (III) for the reaction with an aldehyde ALD of the formula (IV) are particularly suitable for a amines B1 of the formula (III a),

HX ^1a - A ¹ - NH ₂ (III a) where

X ^{1a is} O or S or NR ^8a or NR ⁹ , wherein R ^{8a is} either a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid Group, is, or is a substituent of the formula (III a '), B ¹ - NH ₂ (III a') and A ¹ , B ¹ and R ^{9 have} the meanings already mentioned.

From the reaction of at least one amine B1 of the formula (III a) with at least one aldehyde ALD of the formula (IV), an aldimine of the formula (Ia) is obtained.

Examples of amines B1 are - compounds having one or two primary aliphatic and one secondary amino group, such as, for example, N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, N-hexyl-1,2-ethanediamine, N- (2-ethylhexyl) -1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, 4-amino-methyl-piperidine, 3- (4-aminobutyl) - piperidine, N- (2-aminoethyl) piperazine, diethylenetriamine (DETA), bis-hexamethylenetriamine (BHMT), 3- (2-aminoethyl) aminopropylamine; Di- and triamines from cyanoethylation or Cyanobutylation and subsequent hydrogenation of primary mono- and diamines, for example N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-hexyl-1, 3-propanediamine, N- (2-ethylhexyl) -1, 3-propanediamine, N-dodecyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 3-methylamino-1-pentylamine, 3- Ethylamino-1-pentylamine, 3-butylamino-1-pentylamine, 3-hexylamino-1-pentylamine, 3- (2-ethylhexyl) -amino-1-pentylamine, 3-dodecylamino-1-pentylamine, 3-cyclohexylamino-1 - pentylamine, dipropylenetriamine (DPTA), N3- (3-aminopentyl) -1, 3-pentanediamine, N5- (3-aminopropyl) -2-methyl-1, 5-pentanediamine, N5- (3-amino-1 - ethyl-propyl) -2-methyl-1,5-pentanediamine, and fatty diamines such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine, N-tallowalkylamine. 1, 3-propanediamine, or N- (C _6-22 alkyl) -1, 3-propanediamine, as are obtainable for example under the trade name Duomeen ^® ex Akzo Nobel; the products of the Michael-type addition of aliphatic primary di- or triamines with acrylonitrile, maleic or fumaric diesters, Citraconsäurediestern, acrylic and methacrylic acid esters, acrylic and methacrylic acid amides and Itaconsäurediestern implemented in a molar ratio of 1: 1; Hydroxyamines, such as, for example, 2-aminoethanol, 2-amino-1-propanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino-2-butanol, 2 Amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1-decanol, 12-amino 1-dodecanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-amino-methyl-3,5,5-thmethylcyclohexanol; a primary amino-bearing derivatives of glycols such as diethylene glycol, dipropylene glycol, dibutylene glycol and higher oligomers and polymers of these glycols, for example 2- (2-aminoethoxy) ethanol, 2- (2- (2-aminoethoxy) ethoxy) ethanol, α- (2 -Hydroxymethylethyl) -ω- (2-aminomethylethoxy) -poly (oxy (methyl-1,2-ethanediyl)); a hydroxyl group and a primary amino-bearing derivatives of polyalkoxylated trihydric or higher alcohols; Products from the simple cyanoethylation and subsequent hydrogenation of glycols, for example 3- (2-hydroxyethoxy) propylamine, 3- (2- (2-hydroxyethoxy) ethoxy) propylamine and 3- (6-hydroxyhexyloxy) propylamine; Mercaptoamines such as 2-aminoethanethiol (cysteamine), 3-aminopropanethiol, 4-amino-1-butanethiol, 6-amino-1-hexanethiol, 8-amino-1-octanethiol, 10-amino-1-decanethiol and 12- Annino-i-dodecanethiol.

Preferred as amine B1 are N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, N-methyl-1,3-propanediamine, N-ethyl-1 , 3-propanediamine, N-butyl-1, 3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethylpiperidine, 3- (4-aminobutyl) piperidine, DETA, DPTA, BHMT and fatty diamines such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-ooyloalkyl-1,3-propanediamine and N-tallowalkyl-1,3-propanediamine; Products of the Michael type addition reaction of aliphatic primary diamines with maleic and fumaric diesters, acrylic and methacrylic acid esters, acrylic and methacrylic acid amides, preferably with maleic diesters, in particular maleic acid dimethyl, diethyl, dipropyl and dibutyl esters, and with acrylic acid esters, in particular methyl acrylate, reacted in a molar ratio of 1: 1; and aliphatic hydroxy or mercaptoamines in which the primary amino group are separated from the hydroxyl or mercapto group by a chain of at least 5 atoms, or by a ring, in particular 5-amino-1-pentanol, 6-amino-1 hexanol and higher homologs thereof, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-amino-methyl-3,5,5-thmethyl-cyclohexanol, 2- (2-aminoethoxy) -ethanol, triethylene glycol monoamine and higher oligo- and polymers thereof, 3- (2-hydroxyethoxy) -propylamine, 3- (2- (2-hydroxyethoxy) -ethoxy) -propylamine and 3- (6-hydroxyhexyloxy) -propylamine.

Particular preference is given as amines B1 to amines which are selected from the group consisting of N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, N- Methyl 1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethylpiperidine, 3- (4-aminobutyl ) -piperidine, DETA, DPTA, BHMT, fatty diamines, especially N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyalkyl-1,3-propanediamine and N-tallowalkyl-1 , 3-propanediamine; 5-amino-1-pentanol, 6-amino-1-hexanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol, 2- (2-aminoethoxy) - ethanol, tri- ethylene glycol monoamine, 3- (2-hydroxyethoxy) propylamine, 3- (2- (2-hydroxyethoxy) ethoxy) propylamine and 3- (6-hydroxyhexyloxy) propylamine.

Most preferred amines B1 are amines selected from the group consisting of 5-amino-1-pentanol, 6-amino-1-hexanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3 , 5,5-trimethylcyclohexanol, 2- (2-aminoethoxy) ethanol, ethylene glycol monoamine, 3- (2-hydroxyethoxy) propylamine, 3- (2- (2-hydroxyethoxy) ethoxy) propylamine and 3- (6-hydroxyhexyloxy) propylamine.

As amine B of the formula (III) for the reaction with an aldehyde ALD of

Formula (IV) are particularly suitable for the other amines B2 of the formula (III b),

A ² - ^ NH ₂ ] _t (MI b) where A ² and t have the meanings already mentioned.

From the reaction of at least one amine B2 of the formula (III b) with at least one aldehyde ALD of the formula (IV), an aldimine of the formula (I b) is obtained.

Examples of amines B2 are - aliphatic, cycloaliphatic or arylaliphatic diamines, for example ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,2-propanediamine, 2,2-dimethyl-1,3 Propanediamine, 1, 3-butanediamine, 1, 4-butanediamine, 1, 3-pentanediamine (DAMP), 1, 5-pentanediamine, 1, 5-diamino-2-methylpentane (MPMD), 2-butyl-2-ethyl 1, 5-pentanediamine (C11-neodiamine), 1,6-hexanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD) , 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1, 2, 1, 3 and 1, 4 Diaminocyclohexane, bis (4-aminocyclohexyl) methane (Hi ₂ -MDA), bis (4-amino-3-methylcyclohexyl) methane, bis (4-amino-3-ethylcyclohexyl) methane, bis ( 4-amino-3,5-dimethylcyclohexyl) methane, bis (4-amino-3-ethyl-5-methylcyclohexyl) methane (M-MECA), 1-amino-3-aminomethyl-3,5,5- trimethylcyclohexane (= isophoronediamine or IPDA), 2- and 4-methyl-1,3-di- aminocyclohexane and mixtures thereof, 1, 3 and 1, 4-bis (aminomethyl) cyclohexane, 2,5 (2,6) bis (aminomethyl) bicyclo [2.2.1] heptane (NBDA), 3 ( 4), 8 (9) -bis (aminomethyl) -thcyclo [5.2.1.0 ^{2 6} ] decane, 1, 4-diamino-2,2,6-trimethylcyclohexane (TMCDA), 1, 8-menthanolamine, 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, and 1, 3- and 1, 4-xylylenediamine;

Ether group-containing aliphatic diamines, for example bis (2-aminoethyl) ether, 3,6-dioxaoctane-1, 8-diamine, 4,7-dioxadecane-1, 10-diamine, 4,7-dioxadecan-2 , 9-diamine, 4,9-dioxadodecane-1, 12-diamine, 5,8-dioxadodecane-3,10-diamine and higher oligomers of these diamines, bis (3-aminopropyl) polytetrahydrofurans and other polytetrahydrofuran diamines Molecular weights in the range of, for example, 350 to 5200, and polyoxyalkylene diamines. The latter are typically products from the amination of polyoxyalkylenediols and are obtainable for example under the name Jeffamine ^® (from Huntsman), under the name poly ether amine (from BASF) or under the name PC Amine ^® (from Nitroil). Particularly suitable polyoxyalkylene diamines are Jeffamine ^® D-230, Jeffamine ^® D-400, Jeffamine ^® D-2000, Jeffamine ^® D-4000, Jeffamine ^® XTJ- 511, Jeffamine ^® ED-600, Jeffamine ^® ED-900, Jeffamine ^® ED-2003, Jeffamine ^® XTJ-568, Jeffamine ^® XTJ-569, Jeffamine ^® XTJ-523, Jeffamine ^® XTJ-536, Jeffamine ^® XTJ-542, Jeffamine ^® XTJ-559, Jeffamine ^® EDR-104, Jeffamine ^® EDR 148, Jeffamine ^® EDR-176; Polyetheramine D 230, polyetheramine poly ether amine D 400 and D 2000, PC amines ^® DA 250, PC amines ^® DA 400, DA 650 and PC amines ^® PC amines ^® DA 2000;

aliphatic, cycloaliphatic or arylaliphatic triamines such as 4-amino-methyl-1, 8-octanediamine, 1, 3,5-ths (aminomethyl) -benzene, 1,3,5-ths (amino-methyl) -cyclohexane, Ths- (2-aminoethyl) amine, tris (2-aminopropyl) amine, ths- (3-aminopropyl) amine;

- polyoxyalkylene Thamine which are typically products from the amination of polyoxyalkylenetriols and obtainable for example under the trade name Jeffamine ^® (from Huntsman), under the name polyetheramine (from BASF) or under the name PC Amine ^® (from Nitroil) such as Jeffamine ^® T-403, Jeffamine ^® T-3000, Jeffamine ^® T-5000; Polyetheramine T403, polyetheramine T5000; and PC amines TA 403, TA 5000. PC amines ^® aromatic di- and triamines, such as 1, 2-, 1, 3- and 1, 4- phenylenediamine, 2,4- and 2,6-toluene diamine (TDA), 3,4-toluenediamine, 3,5-dimethylthio-2,4- and -2,6-toluenediamine, 3,5-diethyl-2,4- and -2,6-toluenediamine (DETDA), 2,4,6 -Triethyl-1, 3-phenylenediamine, 2,4,6-triisopropyl-1, 3-phenylenediamine, 3-ethyl-5-methyl-2,4-toluylenediamine, 3,5-diisopropyl-2,4 toluene diamine, 3,5-bis (1-methylpropyl) -2,4-toluene diamine, 3,5-bis (tert-butyl) -2,4-toluene diamine, 3-ethyl-5-isopropyl-2,4 toluene diamine, 5-isopropyl-2,4-toluene diamine, 5- (tert-butyl) -2,4-toluene diamine, 4,6-bis (1-methylpropyl) -1,3-phenylene diamine, 4-isopropyl-6 - (tert -butyl) -1,3-phenylenediamine, 4-ethyl-6-isopropyl-1,3-phenylenediamine, 4-ethyl-6- (2-methylpropyl) -1,3-phenylenediamine, 4-ethyl-6 - (1-methylpropyl) -1,3-phenylenediamine, 4-ethyl-6- (2-methylpropyl) -1, 3-phenylenediamine, 4-isopropyl-6- (1-methylpropyl) -1,3-phenylenediamine , 4- (tert -butyl) -6- (2-methylprop yl) -1, 3-phenylenediamine, 4-cyclopentyl-6-ethyl-1, 3-phenylenediamine, 4-cyclopentyl-6-isopropyl-1,3-phenylenediamine, 4,6-dicyclopentyl-1,3-phenylenediamine, 3 2-methylpropyl- (4-chloro-3,5-diaminobenzoate), tert -butyl- (4-chloro-3,5-diaminobenzoate), 2,6-diaminopyridine, melamine, 4-.isopropyl-2,6-toluene diamine; , 4'-, 2,4'- and 2,2'-diaminodiphenylmethane (MDA), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane (MOCA), 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane (M-DEA), 3,3', 5,5'-tetraethyl-2,2'-dichloro 4,4'-diaminodiphenylmethane (M-CDEA), 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane (M-MIPA), 3,3 ', 5,5'-tetraisopropyl 4,4'-diaminodiphenylmethane (M-DIPA), 3,3 ', 5,5'-tetra (1-methylpropyl) -4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5 '5'-di-tert-butyl-4,4'-diaminodiphenylmethane, 3,3'-di-tert-butyl-4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone (DDS), 4 -Amino-N- (4-aminophenyl) -benzenesulfonamide, 5,5'-methylendianthranileate dimethyl- (5,5'-methylene-dianthranilate), 1,3-propylene-bis (4-aminobenzoate), 1,4-butylene-bis- (4-aminobenzoate), polytetramethylene oxide bis (4-aminobenzoate); aminobenzoate) (available as Versalink ^® from Air Products) and 1, 2-bis (2-aminophenylthio) ethane. - Polyamines with primary aromatic and primary aliphatic

Amino groups, in particular 4-aminoethylaniline, 4-aminomethylaniline,

4 - [(4-aminocyclohexyl) methyl] aniline, 2-aminoethylaniline, 2-aminomethylaniline, 2 - [(4-aminocyclohexyl) methyl] aniline and 4 - [(2-aminocyclohexyl) methyl] aniline.

The amine B2 is preferably selected from the group consisting of 1,6-hexamethylenediamine, MPMD, DAMP, IPDA, TMD, 1,3-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) - methane, bis (4-amino-3-methylcyclohexyl) methane, 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.O ²⁶ ] decane, 1, 2-, 1 , 3- and 1,4-diaminocyclohexane, 1,4-diamino-2,2,6-trimethylcyclohexane, 3,6-dioxaoctane-1,8-diamine, 4,7-dioxadecan-1,10-diamine, 4-amino-methyl-1, 8-octane diamine, polyoxyalkylene-polyamines having two or three amino groups, especially the types available under the trade name Jeffamine ^® D-230, D-400, D-2000, T-403 and T-5000 Huntsman and analogous compounds from BASF or Nitroil; 1, 3 and 1, 4-phenylenediamine, 2,4- and 2,6-toluenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4, 4'-diaminodiphenylmethane and mixtures of said polyamines.

For the preparation of an aldimine of the formula (I), at least one aldehyde ALD of the formula (IV) is furthermore used,

where Y, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meanings already mentioned.

In one embodiment, an aldehyde ALD of formula (IV) is obtainable as the product of a Mannich reaction analogous α-aminoalkylation, as known from the literature. An aldehyde Y 1 of the formula (V), an aldehyde Y 2 of the formula (VI) and a compound C of the formula (VII) are thereby dehydrated to form an aldehyde ALD of the formula (IV).

O ^ R ³ (VI)

In the formulas (V), (VI) and (VII), Y, R ¹ , R ² , R ³ and R ^{4 have} the meanings already mentioned. This reaction can be carried out either with the free reagents Y1, Y2 and C according to the formulas (V), (VI) and (VII), or the reagents can be used partially or completely in dehvatisierter form. In a preferred embodiment, the reaction is carried out with all reagents in free form as a one-pot reaction and the aldehyde ALD purified by distillation after the reaction. Preference is given to using no organic solvents.

Particularly suitable aldehydes Y1 of the formula (V) are the following aldehydes: isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcapronaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2 -Methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde and diphenylacetaldehyde. Isobutyraldehyde is preferred.

Particularly suitable aldehydes Y 2 of the formula (VI) are the following aldehydes: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, phenylacetaldehyde and glyoxylic acid esters, in particular ethyl glyoxylate. Preferred is formaldehyde.

Suitable compounds C of the formula (VII) are, on the one hand, amides, in particular N-methylformamide, N-ethylformamide, N-butylformamide, N-methylacetamide, N-ethylacetamide, N-isopropylacetamide, N-butylacetamide, N-N- (2-ethylhexyl ) acetamide, cyclohexylacetamide, N-benzylacetamide, N-methylpropionamide, N-methylbutyramide, N-methyl-2-ethylcapronamide, N-methyl- benzamide; furthermore lactams and derivatives thereof, in particular 2-pyrrolidone, 5-methyl-2-pyrrolidone, piperidin-2-one, ε-caprolactam, 2-azabicyclo [2.2.1] hept-5-en-3-one; furthermore monosubstituted carbamates and derivatives thereof on the nitrogen atom, in particular O-ethyl-N-methylcarbamate, O-ethyl-N-ethylcarbamate, O-ethyl-N-propylcarbamate, O-methyl-N-ethylcarbamate, O-methyl-N- propyl carbamate, O-methyl-N-butyl carbamate, acetyl urethane, N-butyl urethane, oxazolidin-2-one, oxazolidine-2,5-dione; furthermore imides and derivatives thereof, in particular pyrrolidine-2,5-dione (= succinimide), 3,4-dimethyl-pyrrolidined-2,5-dione, 3,3,4,4-tetramethylpyrrolidine-2,5 -dione, 3-ethyl-3-methyl-pyrrolidinedione-2,5-dione, piperidine-2,6-dione, 4,4-dimethyl-piperidine-2,6-dione, 1,5,5-trimethyl -imidazolidine-2,4-dione, phthalimide, methylphthalimide, hexahydrophthalimide, methylhexahydrophthalimide, 5,5-dimethyl-1,3-oxazolidine-2,4-dione, acetimide; further analogous to above compounds with sulfur instead of oxygen atoms, in particular N-methylthioacetamide, N-butylthioacetamide, N- (2-ethylhexyl) thioacetamide, N-benzylthioacetamide, N-methylbutyrthioamide, N-methyl (2-ethylcapronthioamid), N -Methylbenzothioamide, 2-thiopyrrolidone, O-ethyl-N-methyl-thiocarbamate, S-ethyl-N-methyl-thiocarbamate, O-methyl-N-ethyl-thiocarbamate, thiazolidin-2-one and thiazolidine 2 , 5-dione. Preferably, the compound C is selected from the group consisting of N-methylformamide, N-methylacetamide, N-butylacetamide, N- (2-ethylhexyl) -acetamide, N-benzylacetamide, N-methylbutyramide, N-methyl- (2-ethylcapron-) amide), N-methylbenzamide, O-ethyl-N-methylcarbamate, 2-pyrrolidone, piperidin-2-one, ε-caprolactam, oxazolidin-2-one, thiazolidin-2-one, pyrrolidine-2,5-dione and phthalimide ,

In a further embodiment, an aldehyde ALD of the formula (IV) is obtainable starting from an intermediate ZW1 of the formula (VIII).

In the formula (VIII), R ¹ , R ² , R ³ and R ^{4 have} the meanings already mentioned.

The intermediate ZW1 of the formula (VIII) is also obtainable as the product of a Mannich reaction analogous α-aminoalkylation, in the same manner as described above for the aldehyde ALD, starting from the already mentioned aldehydes Y1 and Y2, but instead of the compound C of the formula (VII) a primary amine of the formula R ⁴ -NH ₂ is used, wherein R ^{4 has} the meaning already mentioned, and wherein the aldehydes Y1 and Y ₂ and the primary amine are used approximately in the molar ratio 1: 1: 1. Particularly suitable primary amines for the preparation of an intermediate ZW1 are primary aliphatic amines, in particular methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, hexylamine, cyclohexylamine, octylamine, 2-ethyl-1-hexylamine, benzylamine, 1 - or 2-phenylethylamine and decylamine. For the preparation of an aldehyde ALD of the formula (IV), the

Intermediate ZW1 are subsequently reacted with a carboxylic acid, preferably in the form of a carboxylic acid chloride, ester or anhydride, to give the corresponding amide, aliphatic or cycloaliphatic carboxylic acids saturated with carboxylic acid being suitable, in particular formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, Valeric acid, isovalehanoic acid, pivalic acid, caproic acid, cyclohexanecarboxylic acid, oleic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capnic acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, isostearic acid and arachic acid; mono- or polyunsaturated aliphatic carboxylic acids, in particular palmitoleic acid, oleic acid, erucic acid, sorbic acid, linoleic acid, linolenic acid, elaeostearic acid, ricinoleic acid and ricinensic acid; aromatic carboxylic acids, in particular benzoic acid and the positionally isomeric toluenes, methoxybenzoic acids and nitrobenzoic acids; and chlorides, esters and anhydrides of said carboxylic acids; and furthermore anhydrides of dicarboxylic acids such as phthalic anhydride, 4-methyl-phthalic anhydride, succinic anhydride, maleic anhydride, citraconic acid anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride and 1, 2,3,6-tetrahydrophthalic anhydride.

For the preparation of an aldehyde ALD of the formula (IV), the intermediate ZW1 can furthermore be reacted with a carbonate or preferably a chloroformate, in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, neopentyl, hexyl, octyl -, 2-ethylhexyl, benzyl, phenyl, ToIyI- and methoxyphenyl chloroformate, are reacted to the corresponding urethane.

For producing an aldehyde ALD of the formula (IV), the intermediate ZW1 further comprising a N, N-disubstituted carbamate or an N, N-disubstituted carbamic acid chloride, such as in particular N ₁ N- dimethyl, N, N-diethyl, N, N-diisopropyl, N, N-dibutyl, N-methyl-N-phenyl and N, N-diphenyl-carbamoyl chloride, and in particular 1-pyrrolidine, 1-piperidine, 1-morpholine and 4-methyl 1 -piperazine-carbonylchlohd, are reacted to the corresponding urea.

For the preparation of an aldehyde ALD of the formula (IV), the intermediate ZW1 can furthermore be reacted with a thiocarboxylic acid, in particular thioacetic acid, thiopropionic acid, thiobenzoic acid, thiotolylic acid or phenylthioacetic acid, preferably in the form of an acid chloride, ester or anhydride, to give the corresponding thioamide.

For producing an aldehyde ALD of the formula (IV), the intermediate ZW1 further thiocarbonate with a (di), chloro (di) thio ameisensäureester, an N, N-disubstituted thiocarbamate or N ₁ N-disubstituted carbamic acid chloride, such as in particular O -Methyl, O-ethyl, O-phenyl or Op-tolyl-chloridothiocarbonat, S-methyl, S-ethyl, S-propyl or S-phenyl-chloridothiocarbonat, Phenylchloridodithiocarbonat, N ₁ N-dimethyl , N, N-diethyl, N-methyl-N-phenyl or N, N-diphenyl-thiocarbamoyl chloride, to the corresponding (di) thiourethan or urea are reacted.

Another way of producing an aldehyde ALD of

Formula (IV) provides the reaction of an aldehyde Y1 of the formula (V), as already mentioned above, with a compound of the formula (IX),

in which

L is a radical selected from the group consisting of a halogen atom, an alkoxy group, a carboxylic acid ester group, a nitrogen-bonded urethane group, a dialkylamino group and a di- or trialkylammonium group, and Y, R ³ , R ⁴ and R ^{5 are} the have already described meanings.

Particularly suitable compounds of the formula (IX) are N-chloro- or N-bromomethyl-N-alkyl-carbamates, such as N-chloromethyl-N-methyl-carbamic acid ethyl ester, and N-bromomethyl-imides, such as N-bromomethyl-phthalimide and N-bromomethyl-pyrrolidine-2,5-dione.

The aldehydes ALD of the formula (IV) have a number of special properties. Due to their chemical structure, they have no or only a slight, amine-like odor, even at a relatively low molecular weight. They are therefore low odor or odor free. Furthermore, they have no hydrogen atom in the α position to the carbonyl C atom. As a result, their aldehyde groups can not tautomehsieren to enol groups and are thus unreactive towards isocyanate groups. Furthermore, in contrast to .beta.-aminoaldehydes, they are not basic, so that they are particularly readily storable together with isocyanate groups, in particular also together with aromatic isocyanate groups. Furthermore, in addition to the aldehyde group, they additionally have functional groups which are capable of forming hydrogen bond bonds. This may be one of the reasons why they are very well tolerated in hydrogen bonding plastic compositions, especially in polyurethane compositions. They do not tend to migrate or sweat there and have little plasticizing effect, which is often very beneficial. The aldehyde ALD of the formula (IV) is preferably selected from the group consisting of N- (2,2-dimethyl-3-oxopropyl) -N-methylformamide, N- (2,2-dimethyl-3-oxopropyl) -N- methylacetamide, N- (2,2-dimethyl-3-oxopropyl) -N-butylacetamide, N- (2,2-dimethyl-3-oxopropyl) -N- (2-ethylhexyl) acetamide, N- (2,2- Dimethyl-3-oxopropyl) -N-benzylacetamide, N- (2,2-dimethyl-3-oxopropyl) -N-methylbutyramide, N- (2,2-dimethyl-3-oxopropyl) -N-methyl- ( 2-ethyl capronanide), N- (2,2-dimethyl-3-oxopropyl) -N-methylbenzannide, O-ethyl-N- (2,2-dimethyl-3-oxopropyl) -N-methylcarbamate, N- ( 2,2-dimethyl-3-oxopropyl) -pyrrolidin-2-one, N- (2,2-dimethyl-3-oxopropyl) -piperidin-2-one, N- (2,2-dimethyl-3-oxopropyl) -azepan-2-one, N- (2,2-dimethyl-3-oxopropyl) -oxazolidin-2-one, N- (2,2-dimethyl-3-oxopropyl) -thiazolidin-2-one, N - (2,2-dimethyl-3-oxopropyl) -pyrrolidine-2,5-dione and N- (2,2-dimethyl-3-oxopropyl) phthalimide.

Preference is given to aldimines of the formula (I) which are obtained from the reaction of either at least one amine B1 of the formula (IIIa) or at least one amine B2 of the formula (IIIb) and at least one of the said preferred aldehydes ALD of the formula (IV ).

A further possibility of obtaining an aldimine of the formula (I) is based on an intermediate ZW 2 of the formula (X)

in which

X ^{2 is} O or S, and m, n, A, R ¹ , R ² , R ³ and R ^{4 have} the meanings already mentioned.

For the preparation of an aldimine of the formula (I), the intermediate ZW2 can be used instead of the intermediate ZW1 of the formula (VIII) either with at least one carboxylic or thiocarboxylic acid, preferably in the form of a carbon or thiocarboxylic acid chloride, ester or anhydride - ing amide or thioamide, or with at least one carbonate or thiocarbonate, preferably in the form of a chloroformate or Chlorthio formic acid ester, are reacted to the corresponding urethane or thiourethane, wherein the same carboxylic or thiocarboxylic acids and carbonates or thiocarbonates are suitable as already described in the reaction with an intermediate ZW1.

The intermediate ZW2 is obtained in particular by the reaction of a corresponding intermediate ZW1 with at least one amine B of the formula (III) in a suitable ratio, but amines B with secondary amino groups are not suitable. Preferred for this reaction are the stated amines B2 and the amines B1 mentioned, in which X ^{1a is} O or S, in particular O.

Those embodiments of aldimines of the formula (I) which have at least one group HX may optionally be in equilibrium with cyclic forms, as shown by way of example in formula (XI) for aldimines of the formula (I) with m = 1. These cyclic forms in the case of aminoaldimines are cyclic aminals, for example imidazolidines or tetrahydropyrimidines; in the case of hydroxyaldimines, cyclic aminoacetals, for example oxazolidines or tetrahydrooxazines; in the case of mercaptoaldimines, cyclic thioaminals, for example thiazolidines or tetrahydrothiazines.

In the formula (XI), n, A, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and Y have the meanings already mentioned. Surprisingly, most HX-containing groups tend to

Aldimines of the formula (I) not for cyclization. In particular, for aminoaldimines can be shown by IR and NMR spectroscopic methods that these compounds predominantly in the open-chain, so the aldimine form, while the cyclic, so the aminal form, does not occur or only in traces. Also, aldimines of the formula (I) derived from hydroxy and mercaptoamines in which the primary amino group of the hydroxyl or the mercapto group are separated by a chain of at least 5 atoms or by a ring, show little cyclization.

The aldimines of the formula (I) are novel, previously undescribed compounds having advantageous properties. They contain tertiary aldimino groups, which therefore have no hydrogen atom in the α-position to the carbonyl group and therefore can not tautomerize to enamino groups. As a result, these aldimino groups are particularly well protected ("blocked") primary amino groups which, with the exclusion of moisture, show no or only extremely low reactivity with compounds which are reactive toward amino groups. Urethane, thiourethane, urea or thiourea group The aldimines of the formula (I) are surprisingly readily storable together with isocyanate groups, in particular also together with aromatic isocyanate groups. Urethane, thiourethane, urea and thiourea groups are barely basic, and furthermore the aldimines of the formula (I) have no or only a slight, amine-like odor, even at a relatively low molecular weight of the underlying aldehyde ALD. that it is in the aldimines of the formula (I) usually u m is liquid compounds.

The aldimines of the formula (I) are storage stable under suitable conditions. Upon ingress of moisture, their aldimino groups can formally hydrolyze to amino groups via intermediates, releasing the corresponding aldehydes ALD of formula (IV) used to prepare the aldimines. Since this hydrolysis reaction is reversible and the chemical equilibrium is clearly on the aldimine side, it can be assumed that, in the absence of amine-reactive compounds, only part of the aldimino groups will be partially or completely hydrolyzed. The aldimines of the formula (I) can be used very widely. They can be used, for example, wherever they can serve as a source of aldehydes ALD of the formula (IV) or of amines B of the formula (III). In particular, they can be used in the function of protected amines, or protected aldehydes, in aldehyde- and / or amine-reactive systems and can be specifically deprotected there if required. In particular, they find application in systems in which compounds are present which react with primary amines. The deprotection is carried out hydrolytically, for example by contact with atmospheric moisture or water, and can be catalyzed by acids.

Aldimines of the formula (I) with m> 0 are still used in the construction of further functionalized reaction products of these aldimines. Thus, aldimines of the formula (I) with m> 0 can be converted into addition products with compounds which can undergo addition reactions with the group HX. Suitable compounds containing such addition reactions carry reactive groups such as, for example, isocyanate groups, epoxide groups, anhydride groups or more or less strongly activated double or triple bonds such as (meth) acrylate groups, acrylamide groups, 1-ethylcarbonyl groups, 1-propynylcarbonyl groups, maleimide groups, citraconimide groups, vinyl groups , Isopropenyl groups or allyl groups. If desired, such aldimino-containing addition products can be hydrolyzed to aldehydes ALD of the formula (IV) and compounds containing primary amino groups and used thereon for further reactions, for example for crosslinking reactions.

Among these addition products are particularly interesting

Addition products AV of the formula (XII) which are obtainable from the reaction of at least one polyisocyanate, in particular a polyisocyanate P, as described in detail later in this document, with at least one aldimine of the formula (Ia).

Where u is O or 1 or 2 or 3, v is 1 or 2 or 3 or 4, with the proviso that (u + v) is 2 or 3 or 4; Q is the radical of a (u + v) isocyanate group

Polyisocyanates P after removal of all isocyanate groups; and A ¹ , X ¹ , Y, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings already mentioned.

Aldimines of the formula (I) and addition products AV of the formula (XII) are particularly suitable for use in compositions based on isocyanates. They can be used, in particular, as latent hardeners or as co-monomers in one- or two-component compositions containing isocyanate groups, which are used as adhesive, sealant, potting compound, coating, floor covering, paint, lacquer, primer or foam.

As already mentioned, the aldimines of the formula (I) and their addition products contain tertiary aldimino groups which do not tautomerize to enamino groups, which are particularly well protected primary amino groups. Together with isocyanate group-containing compounds, the aldimines of the formula (I) can form storage-stable, ie largely viscosity-constant mixtures with the exclusion of moisture, it being considered that the active hydrogen optionally contained in the aldimines (I) reacts with the isocyanate groups and thereby Addition products, such as the addition products AV of the formula (XII) forms. In particular, mixtures which contain free aromatic isocyanate groups are also storage-stable.

A composition of an isocyanate-containing compound and an aldimine of the formula (I) reacts on contact with moisture, in particular in the form of atmospheric moisture, with hydrolysis of the aldimino groups; The isocyanate groups react with the primary amino groups formally released by the hydrolysis of the aldimino groups to form urea groups, an aldehyde ALD being liberated. In relation to The aldimino groups excess isocyanate groups react directly with moisture and also form urea groups. With suitable stoichiometry between isocyanate groups and aldimino groups, the composition will cure as a result of these reactions; This process is also referred to as networking. The reaction of the isocyanate groups with the hydrolyzing aldimino groups need not necessarily take place via free amino groups. Of course, reactions with intermediates of the hydrolysis reaction are possible. For example, it is conceivable that a hydrolyzing aldimino group in the form of a hemiaminal reacts directly with an isocyanate group.

After curing, the released aldehyde ALD remains in the cured composition. It is extremely compatible with this, hardly prone to migration or exudation and has only a low plasticizing effect, which is often very beneficial.

Another object of the invention are curable compositions, also referred to below as polyurethane compositions containing at least one polyisocyanate and at least one aldimine of the formula (I). If the aldimine of the formula (I) has at least one HX group, it may also be present in the form of an addition product, in particular as addition product AV of the formula (XII).

Substance names starting with "poly", such as polyol, polyisocyanate or polyaldehyde, refer in the present document to substances which formally contain two or more of the functional groups occurring in their name per molecule.

The term "polyisocyanate" as used herein

Compounds having two or more isocyanate groups, irrespective of whether they are monomeric diisocyanates, oligomeric polyisocyanates or polymers having a relatively high isocyanate group

Molecular weight acts.

The term "polymer" in the present document comprises, on the one hand, a collective of chemically uniform, but with respect to polymer tion, molecular weight and chain length differing macromolecules, which was prepared by a polyreaction (polymerization, polyaddition, polycondensation). On the other hand, the term also encompasses derivatives of such a collective of macromolecules from polyreactions, compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on given macromolecules and which may be chemically uniform or chemically nonuniform. The term also includes so-called prepolymers, ie reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.

The term "polyurethane polymer" encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyethers Polyureas, polyureas, polyester-polyureas, polyisocyanurates and polycarbodiimides.

The aldimines suitable for use as aldimine of the formula (I) and their preferred embodiments have previously been described in detail. Preferred aldimines of the formula (I) are the aldimines of the formula (Ia) and the aldimines of the formula (Ib). Aldimines of the formula (Ia) in which HX ^{1 is} a hydroxyl or mercapto group, in particular a hydroxyl group, and aldimines of the formula (Ib) are particularly preferred. Most preferred are aldimines of formula (I b).

The polyurethane composition may be one-component or two-component. A two-part polyurethane composition comprises a component K1, which contains at least one polyisocyanate P, as described in detail below, and a component K2, which contains at least one isocyanate-reactive substance. Aldimines of the formula (I) may in principle be present in the component K2 in the case of a two-component polyurethane composition. For aldimines of the formula (I) with an index of m = 0, in particular for aldimines of the formula (I b), this aldimine may be part of the component K1 and / or K2, while Aldimines of the formula (I), such as, for example, the aldimine of the formula (I a) with an index of m ≠ 0 can not be present in the component K2, without a reaction with the polyisocyanate P.

Preferred as a polyurethane composition is a one-component moisture-curing composition comprising a) at least one polyisocyanate P and b) at least one aldimine of the formula (I b), and / or at least one addition product AV of the formula (XII).

As "one-component" in this document is a curable

Composition referred to, in which all components of the composition are stored mixed in the same container, and which is storage stable at room temperature over a longer period, ie not or only slightly changed in their application or use properties by the storage, and which after application by the action of moisture hardens. A "curable composition" is accordingly termed "two-component" in which the two components, that is to say K1 or K2, can each be stored in a separate container in a storage-stable manner.

The polyisocyanate P in one embodiment is an isocyanate group-containing polyurethane polymer PUP.

The term "polyurethane polymer" encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups Examples of polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyethers A suitable polyurethane polymer PUP is obtainable in particular from the reaction of at least one polyol with at least one polyisocyanate, this reaction being possible by the polyol and the polyisocyanate being purified by customary processes, such as polyureas, polyureas, polyureaureas, polyisocyanurates and polycarbodiimides. for example, at temperatures of 50 ⁰ C to 100 ⁰ C, optionally with the concomitant suitable Catalysts are reacted, wherein the polyisocyanate is metered so that its isocyanate groups in proportion to the hydroxyl groups of the polyol in stoichiometric excess are present. Advantageously, the polyisocyanate is metered so that an NCO / OH ratio of 1.3 to 5, in particular one of 1.5 to 3, is maintained. The "NCO / OH ratio" is understood to mean the ratio of the number of isocyanate groups used to the number of hydroxyl groups used. [Polyurethan ein] In the polyurethane polymer PUP, after the reaction of all the hydroxyl groups of the polyol, the content of free isocyanate groups is preferably from 0.5 to 15% by weight. more preferably from 0.5 to 5% by weight.

Optionally, the polyurethane polymer PUP may be made using plasticizers, with the plasticizers used containing no isocyanate-reactive groups.

Examples of suitable polyols for the preparation of a polyurethane polymer PUP are the following commercial polyols or mixtures thereof:

- Polyoxyalkylenpolyole, also called polyether polyols or oligoetherols, which are polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter molecule having two or more active Hydrogen atoms such as water, ammonia or compounds with multiple OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols , Pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A, 1, 1, 1-thmethylolethane, 1,1,1-trimethylolpropane , Glycerol, aniline, as well as mixtures of the aforementioned compounds. Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts can be used (DMC catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides. Particularly suitable are polyoxyalkylenediols or polyoxyalkylenetholes, in particular polyoxyethylene- and polyoxypropylenedi- and -triols.

Especially suitable are polyoxyalkylenediols and -triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range of 1,000 to 30,000 g / mol, and also polyoxypropylenediols and -triols having a molecular weight of 400 to 8,000 g / mol. mol. Also particularly suitable are so-called ethylene oxide-terminated ("EO" endcapped) polyoxypropylene polyols, the latter being specific polyoxypropylene polyoxyethylene polyols obtained, for example, by pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, upon completion of the polypropoxylation reaction with ethylene oxide alkoxylated and thereby have primary hydroxyl groups.

Styrene-acrylonitrile or Acrylnithl-methyl methacrylate grafted polyether polyols.

- Polyester polyols, also called oligoesterols, prepared by known methods, in particular the polycondensation of hydroxycarboxylic acids or the polycondensation of aliphatic and / or aromatic polycarboxylic acids with dihydric or polyhydric alcohols.

Particularly suitable as polyester polyols are those which are prepared from dihydric to trihydric, especially dihydric, alcohols, such as, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl 1, 5-hexanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, 1, 12-hydroxystearyl alcohol, 1, 4-cyclohexanedimethanol, di-fatty acid diol (dimerdiol), Hydroxypivalic acid neopentyl glycol ester, glycehn, 1,1,1-thymethylolpropane or mixtures of the abovementioned alcohols, with organic di- or tricarboxylic acids, in particular dicarboxylic acids, or their anhydrides or esters, such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, suberic acid, Azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, diethyl fatty acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid, trimellitic acid and trimellitic anhydride, or mixtures of the abovementioned acids, as well as polyester polyols from lactones such as ε-caprolactone and starters such as the aforementioned di- or trihydric alcohols.

Particularly suitable polyester polyols are polyester diols.

Polycarbonate polyols, as obtained by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols

Dialkyl carbonates, diaryl carbonates or phosgene are accessible.

At least two hydroxyl-bearing block copolymers which have at least two different blocks with a polyether, polyester and / or polycarbonate structure of the type described above, in particular polyetherpolyesterpolyols.

Polyacrylate and polymethacrylate polyols.

Polyhydroxy-functional fats and oils, for example natural fats and oils, in particular castor oil; or obtained by chemical modification of natural fats and oils - so-called oleochemical - polyols, for example, obtained by epoxidation of unsaturated oils and subsequent ring opening with carboxylic acids or alcohols epoxy polyesters or epoxy polyethers, or obtained by hydroformylation and hydrogenation of unsaturated oils polyols; or from natural fats and oils by degradation processes such as alcoholysis or ozonolysis and subsequent chemical linkage, for example by transesterification or dimehization, of the resulting degradation products or derivatives thereof obtained polyols. Suitable degradation products of natural fats and oils are in particular fatty acids and fatty alcohols and fatty acid esters, in particular the methyl esters (FAME), which can be derivatized by hydroformylation and hydrogenation to hydroxy fatty acid esters, for example.

Polyhydrocarbyl polyols, also called oligohydrocarbonols, such as, for example, polyhydroxy-functional polyolefins, polyisobutylenes, polyisoprenes; polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, such as those produced by Kraton Polymers; polyhydroxy-functional polymers of dienes, in particular of 1,3-butadiene, which may in particular also be prepared from anionic polymerization; Polyhydroxy-functional copolymers of dienes such as 1, 3-butadiene or diene mixtures and vinyl monomers such as styrene, acrylonitrile, vinyl chloride, vinyl acetate, vinyl alcohol, isobutylene and isoprene, for example polyhydroxy-functional acrylonitrile / butadiene copolymers, such as those of epoxides or amino alcohols and carboxyl-terminated acrylo nithl / butadiene copolymers (for example commercially available (under the name Hypro ^® formerly Hycar ^®) CTBN and CTBNX and ETBN of Nanoresins AG, Germany, or Emerald performance Materials LLC) can be produced; and hydrogenated polyhydroxy-functional polymers or copolymers of dienes.

These stated polyols preferably have an average molecular weight of from 250 to 30,000 g / mol, in particular from 400 to 20,000 g / mol, and preferably have an average OH functionality in the range from 1.6 to 3.

Preferred polyols are polyether, polyester, polycarbonate and polyacrylate polyols, preferably diols and triols. Particular preference is given to polyether polyols, in particular polyoxypropylene and polyoxypropylene polyoxyethylene polyols, and to liquid polyester polyols and polyether polyester polyols. In addition to these mentioned polyols, small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, ethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomers Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1, 1, 1-trimethylolethane, 1, 1, 1 -Th- methylolpropane, glycerol, pentaerythritol, sugar alcohols such as XyNt, sorbitol or mannitol, sugars such as sucrose, other higher alcohols, low molecular weight alkoxylation of the aforementioned dihydric and polyhydric alcohols, and mixtures of the aforementioned alcohols in the preparation the polyurethane polymer PUP be used. Similarly, small amounts of polyols having an average OH functionality of more than 3 may be included, for example, sugar polyols.

Aromatic or aliphatic polyisocyanates, in particular the diisocyanates, are used as the polyisocyanate for the preparation of a polyurethane polymer PUP containing isocyanate groups.

Suitable aromatic polyisocyanates are, in particular, monomeric di- or triisocyanates, such as 2,4- and 2,6-toluene diisocyanate, and any desired mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanates. nat and any mixtures of these isomers (MDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), 1, 3 and 1, 4-Phenylendiisocyana- nat, 2,3,5,6-tetramethyl-1, 4 diisocyanatobenzene, naphthalene-1,5-diisocyanate (NDI), 3,3'-dimethyl-4,4'-diisocyanatodiphenyl (TODI), dianisidine diisocyanate (DADI), 1,3,5-this (isocyanatomethyl) benzene, Tris (4-isocyanatophenyl) methane, tris (4-isocyanatophenyl) thiophosphate, oligomers and polymers of the abovementioned isocyanates, as well as any desired mixtures of the aforementioned isocyanates. Preferred are MDI and TDI.

Suitable aliphatic polyisocyanates are, in particular, monomeric di- or triisocyanates, such as 1,4-tetramethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), 2,2,4- and 2,4, 4-trimethyl-1,6-hexamethylene diisocyanate (TMDI), 1,10-decamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, lysine and lysine ester diisocyanate, cyclohexane 1, 3 and -1, 4-diisocyanate, 1-methyl- 2,4- and 2,6-diisocyanato-cyclohexane and any desired mixtures of these isomers (HTDI or H ₆ TDI), 1-isocyanato-3,3,5-thymethyl-5-isocyanatomethylcyclohexane (= isophorone diisocyanate or IPDI ), Perhydro-2,4'- and -4,4'-diphenylmethane diisocyanate (HMDI or Hi ₂ MDI), 1, 4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI), 1, 3 and 1, 4 Bis- (isocyanatomethyl) -cyclohexane, m- and p-xylylene diisocyanate (m- and p-XDI), m- and p-tetramethyl-1,3-and -1,4-xylylene diisocyanate (m- and p-TMXDI) , Bis (1-isocyanato-1-methylethyl) -naphthalene, dimer and trimer fatty acid isocyanates such as 3,6 Bis (9-isocyanatonyl) -4,5-di- (1 -heptenyl) cyclohexene (dimeryl diisocyanate), α, α, α \ α ', α ", α" -hexamethyl-1,3,5 -mesitylentriiso- cyanate, oligomers and polymers of the aforementioned isocyanates, as well as any mixtures of the aforementioned isocyanates. Preferred are HDI and IPDI.

Preference is given to polyurethane polymers PUP with aromatic isocyanate groups.

The polyisocyanate P is in another embodiment

Polyisocyanate PI in the form of a monomeric di- or triisocyanate or an oligomer of a monomeric diisocyanate or a derivative of a monomeric diisocyanate, wherein as monomeric di- or triisocyanate in particular the aforementioned aromatic and aliphatic di- and triisocyanates are suitable.

Particularly suitable polyisocyanates PI are oligomers or derivatives of monomeric diisocyanates, in particular of HDI, IPDI, TDI and MDI. Commercially available types are in particular HDI biurets, for example, as Desmodur ^® N 100 and N 3200 (from Bayer), Tolonate ^® HDB and HDB-LV (Rhodia) and Duranate 24A-100 ^® (by Asahi Kasei); HDI-Isocyanurates, for example as Desmodur ^® N 3300, N 3600 and N 3790 BA (all from Bayer), Tolonate ^® HDT, HDT-LV and HDT-LV2 (from Rhodia), Duranate ^® TPA 100 and THA-100 ( Asahi Kasei) and Coronate HX ^® (from Nippon Polyurethane); HDI uretdiones, for example, as Desmodur ^® N 3400 (Bayer); HDI Iminooxadiazindiones, for example, as Desmodur ^® XP 2410 (Bayer); HDI-allophanates, for example as Desmodur ^® VP LS 2102 (Bayer); IPDI isocyanurates, for example in solution as Desmodur ^® Z 4470 (from Bayer) or in solid form as Vestanat ^® T1890 / 100 (from Degussa); TDI oligomers, for example as Desmodur IL ^® (Bayer); and mixed isocyanurates based on TDI / HDI, for example, as Desmodur HL ^® (Bayer). Also particularly suitable are room-temperature liquid forms of MDI (so-called "modified MDI"), which are mixtures of MDI with MDI Dehvaten, such as MDI carbodiimides or MDI uretonimines or MDI urethanes, known for example under trade names such as Desmodur ^® CD, Desmodur ^® PF, Desmodur ^® PC (all from Bayer), and mixtures of MDI and MDI homologs (polymeric MDI or PMDI), available under trade names such as Desmodur ^® VL, Desmodur ^® VL50, Desmodur ^® VL R10, Desmodur ^® VL R20 and Desmodur ^® VKS 2OF (all from Bayer), Isonate ^® M 309, Voranate ^® M 229 and Voranate ^® M 580 (all manufactured by Dow) (from BASF) or Lupranat ^® M 10 R.

The above-mentioned oligomeric polyisocyanates PI are in practice usually mixtures of substances with different degrees of oligomerization and / or chemical structures. They preferably have an average NCO functionality of 2.1 to 4.0 and in particular contain isocyanurate, iminooxadiazinedione, uretdione, Urethane, biuret, allophanate, carbodiimide, uretonimine or oxadiazinethione groups. These oligomers preferably have a low content of monomeric diisocyanates.

Preferred as the polyisocyanate PI are liquid forms of MDI which are liquid at room temperature, as well as the oligomers of HDI, IPDI and TDI, in particular the isocyanurates and the biurets.

In another embodiment, the polyisocyanate P is a

Mixture consisting of at least one polyurethane polymer PUP and at least one polyisocyanate PI, as described above.

Preferably, the polyisocyanate P is in the form of an aromatic

Isocyanate group-containing polyurethane polymer PUP.

Usually, the polyisocyanate P is present in an amount of from 5 to 95% by weight, preferably in an amount of from 10 to 90% by weight, based on the total composition. In filled compositions, i. Compositions containing a filler, the polyisocyanate P is preferably present in an amount of 5 to 60% by weight, especially 10 to 50% by weight, based on the total composition.

The one-component moisture-curing composition comprises, in addition to at least one polyisocyanate P, at least one aldimine of the formula (I b) and / or an addition product AV of the formula (XII) the latter optionally being formed in situ from at least one aldimine of the formula (Ia) and the polyisocyanate P.

In the one-component moisture-curing composition, the ratio between the sum of the number of aldimino groups and HX groups and the number of isocyanate groups is advantageously 0.1 to 1.1, preferably 0.2 to 0.9, in particular 0.5 to 0.9.

Optionally, the one-component moisture-curing composition contains further constituents, in particular the auxiliaries and additives conventionally used in polyurethane compositions, for example the following:

Plasticizers, in particular carboxylic esters, such as phthalates, in particular dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, in particular dioctyl adipate, azelates and sebacates, organic phosphoric and sulfonic acid esters or polybutenes;

non-reactive thermoplastic polymers, for example homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylates, in particular polyethylenes (PE), polypropylenes (PP) , Polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) and atactic poly-α-olefins (APAO);

- solvents;

inorganic and organic fillers, in particular ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, barite (BaSO ₄ , also called barite), quartz flours, calcined kaolins, aluminum oxides, aluminum hydroxides, silicic acids, in particular finely divided silicas Pyrolysis processes, Russian, in particular industrially produced Russian (hereinafter referred to as "soot"), PVC powder or hollow spheres; - fibers, for example of polyethylene;

Pigments, for example titanium dioxide or iron oxides;

Catalysts which accelerate the hydrolysis of the aldimino groups, in particular acids, in particular organic carboxylic acids, such as benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic and Hexahydromethylphthalsäureanhydhd, silyl esters of organic carboxylic acids, organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids, or mixtures of the aforementioned acids and acid esters;

Catalysts which accelerate the reaction of the isocyanate groups, in particular organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate and dioctyltin dilaurate, bismuth compounds such as bismuth octoate and bismuth tris (neodecanoate), and compounds containing tertiary amino groups such as 2,2'-dimorpholinodiethyl ether and 1,4-diazabicyclo [2.2.2] octane;

Rheology modifiers, in particular thickeners or thixotropic agents, for example urea compounds, polyamide waxes,

Bentonites or fumed silicas;

- blocked amines, for example in the form of ketimines, oxazolidines, enamines or other aldimines;

Drying agents, such as molecular sieves, calcium oxide, highly reactive isocyanates such as p-tosyl isocyanate, orthoformic esters, alkoxysilanes such as tetraethoxysilane, organoalkoxysilanes such as vinylthymethoxysilane, and organoalkoxysilanes which have a functional group in the α-position to the silane group;

Adhesion promoters, in particular organoalkoxysilanes ("silanes") such as, for example, epoxysilanes, vinylsilanes, (meth) acrylsilanes, isocyanatosilanes,

Carbamatosilanes, alkylsilanes, S- (alkylcarbonyl) -mercaptosilanes and aldiminosilanes, as well as oligomeric forms of these silanes;

- stabilizers against heat, light and UV radiation;

- flame-retardant substances; - Surface-active substances such as in particular wetting agents, leveling agents, deaerators or defoamers;

- Biocides such as algicides, fungicides or fungal growth inhibiting substances. It is advantageous when using such further constituents to ensure that they do not greatly impair the storage stability of the composition. This means that during storage these constituents are not allowed to trigger the reactions leading to crosslinking, such as hydrolysis of the aldimino groups or crosslinking of the isocyanate groups, to any significant extent. In particular, this means that all of these ingredients should contain no or at most traces of water. It may be useful to chemically or physically dry certain ingredients before mixing into the composition. The one-component moisture-curing composition preferably contains at least one catalyst. The catalyst is in particular one of said acids, such as benzoic acid or salicylic acid, or one of said metal compounds, or one of said tertiary amines. It may well be advantageous to use different catalysts or different types of catalysts.

The described one-component moisture-curing composition is prepared and stored in the absence of moisture. It is storage stable, i. it may be stored in the absence of moisture in a suitable packaging or arrangement, such as a keg, bucket, bag, cartridge or bottle, for a period of, for example, several months, without being limited in its performance characteristics or properties changed after curing in a relevant for their use extent. Usually, the storage stability is determined by measuring the viscosity or the extrusion force.

As already mentioned, the aldimino groups present in the composition have the property of formally hydrolyzing on contact with moisture to form an aldehyde ALD of the formula (IV) and an amine B of the formula (III), the latter reacting with the isocyanate groups. In relation to the aldimino groups, excess isocyanate groups react directly with moisture and also form urea groups. As a result of these reactions, the composition cures to a solid material; This process is also referred to as networking. The moisture needed for curing can either come from the air (humidity), or the composition can be contacted with a water-containing component, for example, by painting, for example with a smoothing agent, or by spraying, or it can the composition in the application, a water-containing component are added, for example in the form of a water-containing paste, which, for example, via a static mixer, is mixed.

Preferably, the composition is cured by means of atmospheric moisture.

The one-part moisture-curing composition generally cures without the formation of bubbles. The curing rate can be influenced by the type and amount of one or more optionally present catalysts, the temperature prevailing during the curing and the humidity or the amount of added water.

The described one-component moisture-curing composition has a number of advantages. On the one hand, it has good storage stability; In a suitable container, with the exclusion of moisture, it can be kept for several months to a year and remains usable during this time in the intended manner. On the other hand, upon contact with moisture, the composition rapidly and completely cures to a highly elastic, largely tack-free material having high strength, elongation, and high moduli of elasticity. The released upon curing aldehyde ALD of formula (IV) is very well tolerated in the composition. It has little softening effect on the cured composition and tends neither to exude nor to migrate. Even with a relatively low molecular weight of the aldehyde ALD released upon curing, little or no odor occurs before, during and after curing, which is a prerequisite for many applications of such compositions, especially indoors. The compositions described can be used as an adhesive, sealant, coating, floor covering, casting compound, paint, lacquer, primer or foam, in particular as an adhesive, sealant, coating or floor covering. They are particularly suitable for applications in which little or no odor is tolerated and in which elastic properties are required with relatively high moduli of elasticity.

A further aspect of the present invention relates to a method for bonding a substrate S1 to a substrate S2, which comprises the steps of: i) applying the one-component moisture-curing composition to a substrate S1; ii) contacting the applied composition with a substrate S2 within the open time of the composition; or i ') applying the one-component moisture-curing composition to a substrate S1 and to a substrate S2; ii ') contacting the applied composition with each other within the open time of the composition; wherein the substrate S2 is made of the same or a different material as the substrate S1.

The term "open time" in this document refers to the time during which the composition can be processed after the isocyanate groups of the polyisocyanate have come into contact with moisture.

Another aspect of the present invention relates to a method of sealing. This comprises the step of applying the one-component moisture-curing composition between a substrate S1 and a substrate S2 such that the composition is in contact with the substrate S1 and the substrate S2, the substrate S2 being made of the same or a different material Material as the substrate S1 exists. Usually, the sealant is pressed into a so-called joint.

Another aspect of the present invention relates to a method of coating a substrate S1. This comprises the step: i "') applying the one-component moisture-curing composition to a substrate S1 within the open time of the composition.

In these methods, suitable substrates S1 and / or S2 are in particular

- glass, glass ceramic, concrete, mortar, brick, brick, plaster and natural stones such as granite or marble;

- metals or alloys such as aluminum, steel, iron, non-ferrous metals, galvanized metals; - Leather, textiles, paper, wood, resin-bonded wood-based materials, resin-textile composites and other so-called polymer composites;

- plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding compounds), polycarbonate (PC), polyamide (PA), polyester, poly (methyl methacrylate) (PMMA) , Polyesters, epoxy resins, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), polyethylene (PE) or polypropylene (PP), ethylene / propylene copolymers (EPM) and ethylene / propylene / diene terpolymers (EPDM ), wherein the plastics may preferably be surface treated by means of plasma, corona or flame; coated substrates such as powder-coated metals or alloys; as well as paints and varnishes.

If necessary, the substrates can be pretreated before applying the composition. Such pretreatments include in particular physical and / or chemical cleaning processes, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.

The application of the composition can be carried out in a wide temperature range. For example, the composition at Room temperature can be applied. The composition can also be applied at lower as well as at higher temperatures.

From these described methods for bonding, sealing or coating - or from the use of one of the described compositions as an adhesive, sealant, potting compound, coating, flooring, paint, paint, primer or foam - creates an article.

This article is in particular a building, in particular a building of civil engineering, or an industrial good or a consumer good, in particular a window, a household machine, or a means of transport, in particular a vehicle on water or on land, preferably an automobile, a bus , a truck, a train or a ship, or an attachment of a means of transport, or an article of the furniture, textile or packaging industry.

Examples

Description of the measuring methods

Infrared spectra were measured on a FT-IR 1600 device from Perkin-Elmer (horizontal ATR measuring unit with ZnSe crystal). Liquid samples were applied neat as films, solid samples were dissolved in CH ₂ Cb. The absorption bands are given in wavenumbers (cm ^"1 ) (measurement window: 4000-650 cm ^{" 1} ).

¹ H NMR spectra were measured on a Bruker DPX-300 spectrometer at 300.13 MHz; the chemical shifts δ are given in ppm relative to tetramethylsilane (TMS), coupling constants J are given in Hz. True and pseudo-coupling patterns were not distinguished.

The viscosity was measured on a thermostatically controlled cone-plate viscometer Physica UM (cone diameter 20 mm, cone angle 1 °, cone tip-plate distance 0.05 mm, shear rate 10 to 1000 s ^-1 ) The amine content, ie the total content at aldimino groups and free amino groups in the compounds prepared, was determined by titration (with 0.1 N HCIO ₄ in glacial acetic acid, against crystal violet) and is always given in mmol N / g. Production of aldehydes

N- (2,2-dimethyl-3-oxopropyl) -N-methylacetamide

20.0 g (0.17 mol) of 2,2-dimethyl-3-methylamino-propanal were initially introduced into a round-bottomed flask with reflux condenser under nitrogen atmosphere and with stirring. For this purpose, 30.0 g (0.52 mol) of acetic anhydride were slowly added dropwise, the mixture with 0.1 g of para-toluenesulfonic acid and heated to 120 ⁰ C for 1 hr. After cooling to room temperature, the reaction mixture was mixed with 100 ml of water, neutralized with Na ₂ CO ₃ , extracted several times with ethyl acetate, the combined organic phase dried over MgSO ₄ and concentrated. The resulting brown oil was fractionated in vacuo. The product distilled at a head temperature of 93-95 ⁰ C and a pressure of 3 mbar. Yield: 8.2 g (30% of theory) of colorless and almost odorless liquid, which crystallized on standing. IR: 3418br, 2971, 2939, 2875, 2815, 1786, 2726, 2711 (CHO), 1718 (C = O aldehyde), 1624 (C = O amide), 1487, 1464, 1405, 1364, 1320, 1263, 1202 , 1125, 1108, 1086, 1040, 1007, 973, 951, 923, 904, 873, 772, 733.

N- (2,2-dimethyl-3-oxopropyl) pyrrolidine-2-one

40.0 g (0.48 mol) of 2-pyrrolidinone, 39.2 g (0.48 mol), were placed in a round-bottomed flask with reflux condenser under a nitrogen atmosphere.

36% aqueous formaldehyde and 37.3 g (0.52 mol) of isobutyraldehyde submitted with good stirring with 10.0 g conc. Hydrochloric acid added, the

Mixture boiled vigorously. After the cooking had calmed, the mixture was boiled in an oil bath (100 ^° C.) and boiled overnight. The yellow, clear reaction mixture was neutralized with 2N NaOH, extracted twice with ethyl acetate, the combined organic

Washed with brine, dried over MgSO ₄ and on

Rotary evaporator completely concentrated. The resulting dark yellow oil was fractionated in vacuo. The product distilled at a head temperature of 71 ⁰ C and a pressure of 2-10 ^"2 mbar. Yield: 14.8 g (19% of theory) of colorless and virtually odorless liquid.

IR: 3429br, 2969, 2961 sh, 2930, 2897, 2872, 2837sh, 2786, 2758, 2711 (CHO), 1720 (C = O aldehyde), 1678 (C = O amide), 1494, 1462, 1438sh, 1421, 1400, 1380, 1365, 1333, 1314, 1286, 1259, 1225, 1 152, 1 103, 1062, 1024, 1002, 992, 975, 935, 908, 890sh, 867, 772, 672.

¹ H-NMR (CDCl ₃ , 300 K): δ 9.58 (s, 1 H, CHO), 3.41 (s, 2 H, NCH ₂ C (CH ₂ ) ₂ ), 3.33 {t, J = 7.0, 2 H, NC (O) CH ₂ CH ₂ CH ₂ ), 2.36 {t, J = 8.1, 2H, NC (O) CH ₂ CH ₂ CH ₂ ), 1.99 (m, 2H, NC (O) CH ₂ CH ₂ CH ₂ ), 1.10 (s, 6H, NCH ₂ C (CHs) ₂ ).

N- (2,2-dimethyl-3-oxopropyl) -azepane-2-one

80.5 g (0.71 mol) of ε-caprolactam, 59.3 g (0.71 mol) were placed in a round-bottomed flask with reflux condenser under a nitrogen atmosphere.

36% aqueous formaldehyde and 56.4 g (0.78 mol) of isobutyraldehyde submitted with good stirring with 13.4 g conc. Hydrochloric acid (slight

Exothermic). The mixture was then boiled in an oil bath (100 ^° C.) and boiled overnight. The yellowish, clear reaction mixture was neutralized with 2N NaOH, extracted twice with ethyl acetate, the combined organic phases were washed with brine, dried over MgSO ₄ and concentrated completely on a rotary evaporator. The resulting yellow oil was fractionated in vacuo. The product distilled at a head temperature of 98 ⁰ C and a pressure of 4-10 ^"2 mbar. Yield: 20.7 g (15% of theory) of colorless and odorless liquid which crystallized on standing.

IR: 3415br, 2961, 2926, 2855, 2717 (CHO), 1720 (C = O aldehyde), 1635 (C = O amide), 1479, 1456, 1443, 1419, 1398, 1365, 1353, 1329, 1310, 1292sh , 1258, 1222, 1 197, 1 183, 1157, 1 137, 1 121, 1083, 1060, 1021, 998, 975, 969sh, 954, 944, 923, 909, 890, 872, 839, 815, 771, 735 , 723, 703. 1 H-NMR (CDCI _3, 300 K): δ 9:55 (s, 1 H, CHO), 3:47 (s, 2 H, NCH ₂ C (CHs) _2), 3:36 (m, 2 H, NC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 2.52 (m, 2 H, NC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 1.67 (m, 6 H, NC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 1.09 (s, 6H, NCH ₂ C (CHs) ₂ ). N- (2,2-dimethyl-3-oxopropyl) -N-methylformamide

59.7 g (1.00 mol) of N-methylformamide, 84.3 g (1.00 mol) of 36% strength aqueous formaldehyde and 78.6 g (1.10 mol) of isobutyraldehyde were introduced into a round bottom flask with reflux condenser under a nitrogen atmosphere. place with vigorous stirring with 18.2 g conc. Hydrochloric acid added (slight exothermic). The mixture was then boiled in an oil bath (100 ^° C.) and boiled overnight. The yellow, clear reaction mixture was cooled to room temperature, neutralized with 2N NaOH, extracted twice with ethyl acetate, the combined organic phases were washed with brine, dried over MgSO ₄ and concentrated completely on a rotary evaporator. The resulting dark yellow oil was fractionated in vacuo. The product distilled at a head temperature of 63 ⁰ C and a pressure of 4-10 ^"2 mbar. Yield: 20.2. G (14% of theory) of colorless, slightly pungent liquid IR: 3412br, 2963, 2931, 2872, 2815sh, 2710 (CHO), 1724 (C = O aldehyde), 1667 (C = O amide), 1471, 1444, 1426sh, 1395, 1365, 1302, 1275, 1254, 1181, 1142, 1100, 1071 sh, 1047, 990, 973, 953, 914, 883, 858, 772, 747, 710.

Preparation of Aldimines Example 1 Aldimine A-1

2.91 g (18.5 mmol) of N- (2,2-dimethyl-3-oxopropyl) -N-methylacetamide were placed in a round-bottomed flask under nitrogen atmosphere and 1.28 g (15.4 mmol N) of 1,6-hexamethylenediamine solution (70 % By weight in water, amine content 12.16 mmol N / g). Thereafter, the mixture was heated in an oil bath and the volatiles were removed in vacuo (10 mbar, 80 ⁰ C). Yield: 3.45 g pale yellow, almost odorless oil with an amine content of 4.74 mmol N / g and a viscosity of 630 mPa · s at 20 ° C. IR: 2959, 2930, 2854, 2827sh, 1644 (C = O, C = N), 1484, 1460, 1430, 1400, 1362, 1312, 1262, 1200, 1181 sh, 1120, 1109, 1086, 1030, 1016, 978, 938, 904, 894, 860, 788, 764, 730.

Example 2: Aldimine A-2

Under the same conditions as described for aldimine A-1

10.00 g (59 mmol) of N- (2,2-dimethyl-3-oxopropyl) -pyrrolidin-2-one with 4.00 g (49 mmol of N) of 1,6-hexamethylenediamine (70% in water, amine content 12.16 mmol

N / g). Yield: 11.57 g light yellow, almost odorless oil with a

Amine content of 4.13 mmol N / g and a viscosity of 2.0 Pa-s at 20 ⁰ C. IR: 3410br, 2957, 2927, 2854, 2830sh, 1682 (C = O), 1666sh (C = N), 1493, 1461, 1434sh, 1418, 1392, 1363, 1331, 1313, 1284, 1261, 1222, 1150, 1108, 1057, 1023, 993, 944sh, 934, 911, 883, 854, 787, 758, 728, 675, 665.

¹ H-NMR (CDCl ₃ , 300 K): δ 7.56 {t, J = 1.3, 2H, CH = N), 3.36 {t, J = 7.0, 4H, NC (O) CH ₂ CH ₂ CH ₂ ), 3:35 (fxd, J = 7.0 / 1.3, 4 H, CH = NCH _2), 3:32 (s, 4 H, NCH ₂ C (CHs) _2), 2:34 {t, J = 8.1, 4 H, NC (O) CH ₂ CH ₂ CH ₂ ), 1.97 (m, 4H, NC (O) CH ₂ CH ₂ CH ₂ ), 1.55 (m, 4H, CH = N-CH ₂ CH ₂ ), 1.30 ( m, 4 H, CH = N-CH ₂ CH ₂ CH ₂ ), 1.09 (s, 12 H, NCH ₂ C (CHs) ₂ ). Example 3: Aldimine A-3

12.67g (64 mmol) of N- under the same conditions as described for aldimine A-1 (2,2-dimethyl-3-oxopropyl) -azepane-2-one with 6:46 g (53 mmol N) polyether diamine (Jeffamine ^® D 230, Huntsman; amine content implemented 8.29 mmol N / g) and under high vacuum (4-10 ^"2 mbar) at 120 ⁰ C until constant weight concentrated yield: 16.50 g of yellow, odorless honey with an amine content of 3.18 mmol N /. g and a viscosity of 23.5 Pa-s at 20 ⁰ C. IR: 3420br, 2964, 2927, 2856, 1645 (C = O and C = N), 1480, 1465sh, 1455, 1444, 1417, 1392, 1367, 1328 , 1310, 1291, 1260, 1228, 1196, 1133sh, 1104, 1096sh, 1084sh, 1015, 992, 975, 953, 939, 913, 879, 839, 817, 784, 735, 706. ¹ H-NMR (CDCl ₃ , 300 K): δ 7.58 (m, 2H, CH = N), 3.6-2.8 (m, ca. 19.6H, NCH ₂ C (CHs) ₂ ) and NC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ and N / OCH ₂ CH (CH ₃ )), 2.50 (m, 4 H, NC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 1.75-1.55 (m, 12 H, NC (O) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ), 1.15-1.05 (m, ca. 23.6 H, NCH ₂ C (CHs) ₂ and

N / OCH ₂ CH (CH ₃ )).

Example 4: Aldimine A-4

10.45 g (73 mmol) of N- (2,2-dimethyl-3-oxopropyl) -N-methylformamide with 5.05 g (61 mmol of N) of 1,6-hexamethylenediamine solution ( 70% in water, amine content 12.16 mmol N / g). Yield: 11:54 yellowish, slightly pungent oil which has an amine content of 5.03 mmol N / g and a viscosity of 1010 mPa-s at 20 ⁰ C. IR: 3430br, 2955, 2926, 2855, 2829, 1727, 1666 (C = O, C = N), 1465, 1443sh, 1424, 1390, 1362, 1339sh, 1303, 1273, 1254, 1221 sh, 1182, 1162sh. 1143, 1093, 1067sh, 1046, 992, 975sh, 953, 932sh, 914, 865, 789, 744, 710, 658.

Example 5: Aldimine A-5

Under the same conditions as described for aldimine A-1, 10.00 g (59 mmol) of N- (2,2-dimethyl-3-oxopropyl) -pyrrolidin-2-one were treated with 5.07 g (48 mmol of N) of 2- (2-aminoethoxy ) ethanol (dGA; Diglycolamine ^® agent, Huntsman; Anni content reacted 9:46 mmol N / g). Yield: 14.11 g of pale yellow, almost odorless oil-free with an amine content of 3.39 mmol N / g and a viscosity of 630 mPa-s at 20 ⁰ C.

IR: 3400br (OH), 2958, 2925, 2908, 2867, 1680sh (C = O), 1664 (C = N), 1493, 1463, 1438, 1421, 1393, 1363, 1332, 1314, 1287, 1262, 1226 , 1123, 1060, 1024sh, 991, 946, 934, 899, 885, 858, 814, 788, 759, 674sh, 669. 1 H NMR (CDCl ₃ , 300 K): δ 7.64 {t, J = 1.3, 1 H, CH = N), 3.71 and 3.57 (2 ^χ m, 2x4 H, HOCH ₂ CH ₂ OCH ₂ CH ₂ N), 3.40 {t, J = 7.0, 2 H, NC (O) CH ₂ CH ₂ CH ₂ ), 3.31 (s, 2 H, NCH ₂ C (CHs) _2), 2:35 {t, J = 8.1, 2 H, NC (O) CH ₂ CH ₂ CH _2), 1.98 (m, 2 H, NC ( O) CH ₂ CH ₂ CH ₂ ), 1.11 (s, 6H, NCH ₂ C (CHs) ₂ ). Preparation of curable compositions

Examples 6 to 10 and Comparative Example 11:

In a screw-capped polypropylene cup, either the polyurethane polymer P1 or the polyurethane polymer P2, whose

Preparation is described below using a centrifugal mixer (SpeedMixer ™ DAC 150, FlackTek Inc, 1 min at 2500 rpm)

Aldimine and mixed with catalysts to a homogeneous mass, the resulting mass immediately filled into an internally painted aluminum tube and sealed airtight. The polyurethane polymers, aldimines and catalysts used for each of the examples are listed in Table 1 in parts by weight.

The polyurethane polymer P1 was prepared as follows: 4000 g of polyoxypropylene diol (Acclaim ^® 4200 N, Bayer; OH number 28.5 mg KOH / g) and 520 g of 4,4'-methylene diphenyl diisocyanate (4,4'-MDI; Desmodur ^® 44 MC L, Bayer) were reacted by known method at 80 ⁰ C to an NCO-terminated polyurethane polymer having a content of free isocyanate groups of 1 .9 wt .-%.

The polyurethane polymer P2 was prepared as follows: 590 g of polyol Acclaim ^® 4200 N (polypropylene oxide diol having an OH number of 28.5 mg KOH / g; Bayer), 1 180 g of polyol Caradol ^® MD34-02 (polypropylene oxide-polyethylene Thol, OH number of 35.0 mg KOH / g; Shell) and 230 g of isophorone diisocyanate (IPDI; Vestanat ^® IPDI, Degussa) were by weight by a known method at 80 ⁰ C to give an NCO-terminated polyurethane polymer having a content of free isocyanate groups of 2.1. -% implemented.

Table 1: Composition of Examples 6 to 11. a 5% by weight of dibutyltin dilaurate in diisodecyl phthalate. ^b ratio between the number of aldimino groups and the number of isocyanate groups. ^c ratio of the sum of the number of aldimino groups and HX groups to the number of isocyanate groups.

The compositions thus obtained were tested as follows:

As a measure of storage stability, the change in viscosity during storage in the heat was determined. For this purpose, the composition was stored in the sealed tube in the oven at 60 ⁰ C and the viscosity at 20 ⁰ C a first time after 4 hours (= "viscosity after 4h") and a second time after 7 days (= "viscosity after 7d" ) Storage time measured. The storage stability results from the percentage increase of the second viscosity value compared to the first. For this purpose, the viscosity increase in% is calculated according to the following formula: [(viscosity after 7 d / viscosity after 4 h) - 1] ^χ 100%. To measure the skinning time (time to tack-free, "tack-free time"), a small portion of the stored at 60 ⁰ C for 4 hours composition was applied to cardboard in a layer thickness of about 2 mm and in standard atmosphere (23 ± 1 ⁰ C, 50 ± 5% relative humidity) determined the time it took for the first time, when lightly tapping the surface of the composition by means of an LDPE pipette, that no residues remained on the pipette.

To determine the mechanical properties, films of about 3 mm thickness were produced with the main part of the composition by pouring the composition into a planar PTFE mold and curing it for 7 days under standard conditions. Clear, tack-free and elastic polyurethane films were obtained, which were completely bubble-free. Dumbbells with a length of 75 mm, with a web length of 30 mm and a web width of 4 mm, were punched out of the films and tested for tensile strength, elongation at break and modulus of elasticity (at 0.5-5% elongation) in accordance with DIN EN 53504 ( Pulling speed: 200 mm / min).

In addition, blistering was judged qualitatively (based on the amount of bubbles that occurred during the curing of the film) and the odor. The results of these tests are listed in Table 2.

Table 2: Properties of Examples 6 to 11. n.b. stands for "not determined" (too many bubbles).

Claims

claims

1. Aldimine of Formula (I)

in which

Y is O or S;

A represents either the (n + m) -value radical of an amine after removal of n primary amino groups and m HX groups, or together with R ^{7 represents} an (n + 2 * m) -valent hydrocarbon radical having 3 to 20 C- Atoms which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen;

R ¹ and R ² are each independently of one another in each case a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 4 to 12 C atoms, the part of an optionally substituted, carbo-cyclic ring with 5 to 8, preferably 6, C atoms are;

R ^{3 represents} a hydrogen atom or an alkyl, cycloalkyl, arylalkyl or

Alkoxycarbonylrest having 1 to 12 carbon atoms;

R ⁴ and R ^{5 are} either together for an optionally oxygen or sulfur atoms having divalent radical having 2 to 10 carbon atoms, which is part of an optionally substituted, 5- or 6- or 7-membered ring, are, or

R ^{4 is} an alkyl, cycloalkyl, arylalkyl or acyl radical having 1 to 10 C atoms, and R ^{5 represents} a hydrogen atom or a monovalent radical having 1 to 20 C atoms selected from the group consisting of alkyl, cycloalkyl, arylalkyl, aryl radical, -OR ^{5 '} , -SR ^5' and -NR ^{5 '} R ^{5 ",} wherein R ⁵ and R ⁵ are either each serstoffrest for a hydrocar- or together represent an alkylene group forming part of a 5-, 6- or 7-membered ring, stand; X is O or S or NR ^6, or NR ⁷ where R ^{6 is} either a monovalent hydrocarbon radical having 1 to 20 C

Atoms which optionally has at least one carboxylic acid ester, nitrile, nitro, phosphonic ester, sulfonic or sulfonic acid ester group, is, or represents a substituent of the formula (II),

wherein p is 0 or an integer from 1 to 10OOO, and B is a (p + 1) -valent hydrocarbon radical which optionally contains ether oxygen, tertiary amine nitrogen, hydroxyl groups, secondary amino groups or mercapto groups; and

R ⁷ together with A represents an (n + 2 * m) -valent hydrocarbon radical having 3 to 20 C atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen; n is 1 or 2 or 3 or 4, and m is 0 or 1 or 2 or 3 or 4, with the proviso that m + n is 2 or 3 or 4 or 5.

2. aldimine according to claim 1, characterized in that R ^{4 is} a methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, cyclohexyl or benzyl radical, and that R ^{5 is} hydrogen or a Methyl, ethyl, propyl, isopropyl, butyl, 2-ethylhexyl, cyclohexyl, benzyl, methoxy, ethoxy,

Propoxy or isopropoxy stands.

3. aldimine according to claim 1, characterized in that R ⁴ and R ⁵ together - including the nitrogen atom and the carbonyl group or thiocarbonyl group - a 2-pyrrolidone ring, a pyrrolidine-2,5-dione ring, a pipehdine 2-one ring, a pipehdin-2,6-dione ring, an azepan-2-one ring, an oxazolidin-2-one ring or a thiazolidin-2-one ring, such ring optionally substituted is, form.

4. aldimine according to claim 1 to 3, characterized in that this is an aldimine of the formula (I a),

in which

A ^{1 is} either a divalent hydrocarbon radical having 2 to 20 C atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen, is, or together with R ^{9 is} a trivalent hydrocarbon radical with third to 20 carbon atoms, which optionally at least one

Heteroatom, especially in the form of ether oxygen or tertiary amine nitrogen; X ^{1 is} O or S or NR ⁸ or NR ⁹ , where R ^{8 is} either for a monovalent hydrocarbon radical having 1 to 20 C atoms, which optionally has at least one carboxylic acid ester, nitrile, nitro, phosphonic acid ester, sulfonic or sulfonic acid ester group, or represents a substituent of the formula (II a),

where B ^{1 is} a bivalent, optionally ether

Oxygen or tertiary amine nitrogen, hydrocarbon radical having 2 to 12 carbon atoms; and R ⁹ together with A ^{1 is} a trivalent hydrocarbon radical having 3 to 20 C atoms, which optionally contains at least one heteroatom, in particular in the form of ether oxygen or tertiary amine nitrogen; with the proviso that A ^{1 has} no active hydrogen.

Aldimine according to claim 4, characterized in that it consists of the reaction of at least one amine B1 selected from the group consisting of N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-cyclohexyl-1, 2-ethanediamine, N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethyl- piperidine, 3- (4-aminobutyl) -piperidine, diethylenetriamine (DETA), dipropylenethamine (DPTA), bis-hexamethylenethamine (BHMT), fatty diamines, in particular N-cocoalkyl-1,3-propanediamine, N-oleyl-1, 3-propanediamine, N-soyalkyl-1,3-propanediamine and N-tallowalkyl-1,3-propanediamine; 5-amino-1-pentanol, 6-amino-1-hexanol, 4- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3,5,

5-trimethyl-cyclohexanol,

2- (2-aminoethoxy) ethanol, ethylene glycol monoamine, 3- (2-hydroxyethoxy) propylamine, 3- (2- (2-hydroxyethoxy) ethoxy) propylamine and 3- (6-hydroxyhexyloxy) propylamine is obtained with at least one aldehyde ALD of formula (IV)

6. aldimine according to claim 1 to 3, characterized in that this is an aldimine of the formula (I b),

where t is 2 or 3;

A ^{2 is} the radical of an amine B2 after removal of t primary amino groups, with the proviso that the aldimine of the formula (I b) has no active hydrogen.

7. aldimine according to claim 6, characterized in that the amine B2 is selected from the group consisting of 1, 6-hexamethylenediamine, 1, 5-diamino-2-methylpentane (MPMD), 1, 3-pentanediamine (DAMP), 1 - Amino-3-aminomethyl-3,5,5-trimethylcyclohexane (= isophorone diamine or IPDA), 2,2,4- and 2,4,4-thmethylhexamethylenediamine (TMD), 1, 3-xylylenediamine, 1, 3 Bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) -methane, 3 (4), 8 (9) -bis (amino-methyl) - thcyclo [5.2.1.0 ² ' ⁶ ] decane, 1, 2, 1, 3 and 1, 4-diaminocyclohexane, 1, 4-diamino-2,2,6-thmethylcyclohexane, 3,6-dioxaoctane-1, 8 -diamine, 4,7-dioxadecane-1, 10-diamine, 4-aminomethyl-1,8-octanediamine, polyoxyalkylene polyamines having two or three amino groups, 1, 3 and 1, 4-phenylenediamine, 2 , 4- and 2,6-toluenediamine, 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane and mixtures of said polyamines.

8. aldimine according to one of the preceding claims, obtained from the reaction of at least one amine B1 or B2 with at least one aldehyde ALD of the formula (IV)

selected from the group consisting of N- (2,2-dimethyl-3-oxopropyl) -N-methylformamide, N- (2,2-dimethyl-3-oxopropyl) -N-methylacetamide, N-

(2,2-dimethyl-3-oxopropyl) -N-butylacetamide, N- (2,2-dimethyl-3-oxopropyl) -N- (2-ethylhexyl) acetamide, N- (2,2-dimethyl- 3-oxopropyl) -N-benzylacetamide, N- (2,2-dimethyl-3-oxopropyl) -N-methylbutyramide, N- (2,2-dimethyl-3-oxopropyl) -N-methyl- ( 2-ethylcaproamide), N- (2,2-dimethyl-3-oxopropyl) -N-methylbenzamide, O-ethyl-N- (2,2-dimethyl-3-oxopropyl) -N-methylcarbamate, N - (2,2-dimethyl-3-oxopropyl) -pyrrolidin-2-one, N- (2,2-dimethyl-3-oxopropyl) -piperidin-2-one, N- (2,2-dimethyl- 3-oxopropyl) -azepan-2-one, N- (2,2-dimethyl-3-oxopropyl) -oxazolidin-2-one, N- (2,2-dimethyl-3-oxo-propyl) -thiazolidine-2 -on, N- (2,2-dimethyl-3-oxopropyl) -pyrrolidine-2,5-dione and N- (2,2-dimethyl-3-oxopropyl) phthalimide.

9. aldimine according to any one of the preceding claims, characterized in that it is obtained starting from an intermediate ZW2 of the formula (X),

where X ^{2 is} O or S.

10. Addition product AV of the formula (XII) obtained from the reaction of at least one polyisocyanate P with at least one aldimine of the formula (Ia) according to one of Claims 4 or 5 or 8,

wherein Q is the residue of a (u + v) isocyanate group-containing polyisocyanate P after removal of all isocyanate groups; u is 0 or 1 or 2 or 3, v is 1 or 2 or 3 or 4, with the proviso that (u + v) stands for 2 or 3 or 4.

11. One-component moisture-curing composition comprising a) at least one polyisocyanate P and b) at least one aldimine of the formula (I b) according to any one of claims 6 to 8 and / or at least one addition product AV of

Formula (XII) according to claim 10.

12. One-component moisture-curing composition according to claim 11, characterized in that the polyisocyanate P is an aromatic isocyanate group-containing polyurethane polymer PUP, which is obtainable by the reaction of at least one polyol with at least one aromatic monomeric diisocyanate.

13. A method of bonding a substrate S1 to a substrate S2 comprising the steps of i) applying a one-component moisture-curing composition according to claim 11 or 12 to a substrate S1; ii) contacting the applied composition with a

Substrate S2 within the open time of the composition; or i ') application of a one-component moisture-curing composition according to claim 11 or 12 to a substrate S1 and to a substrate S2; ii ') contacting the applied composition with each other within the open time of the composition; wherein the substrate S2 is made of the same or a different material as the substrate S1.

14. Cured composition obtained from the reaction of a one-part moisture-curing composition according to

Claim 11 or 12 with moisture, in particular in the form of humidity.

15. Use of an aldimine of the formula (I) according to any one of claims 1 to 9 or an addition product AV of the formula (XII) according to

Claim 10 in adhesives, sealants, coatings or floor coverings.